Method of treating textile materials



United States Patent METHOD OF TREATING TEXTILE MATERIALS William J. Vullo, Tonawanda, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Filed May 28, 1965, Ser. No. 459,932 Int. Cl. D06m 1/00 US. Cl. 8-1l6 14 Claims ABSTRACT OF THE DISCLOSURE Textile material treatment to improve the wrinkle resistance thereof by reacting the textile material, in the presence of a basic catalyst, with a polyvinyl phosphine oxide having the formula wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl radicals and R is selected from the group consisting of hydrogen, lower alkyl and lower alkenyl radicals.

This invention relates to improved textile materials and to methods for making the same. In particular, it relates to a method of treating textile material with polyvinyl phosphine oxides to impart wrinkle resistance and other desirable properties to the material.

The process of the present invention comprises reacting a textile material with a polyvinyl phosphine oxide of the formula:

wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl radicals and R is selected from the group consisting of hydrogen, lower alkenyl and lower alkyl radicals. The presence of a basic catalyst significantly promotes chemical reaction.

Textile materials which may be modified in accordance with the present invention include those comprising natural or syn hetic polymers, or blends of the same, possessing functional groups such as hydroxyl, amine, amido, carboxyl, thiol, and the like, which are capable of reaction with vinyl groups activated by attachment to meta directing groups. Suitable polymeric materials include, for example, cellulosic material, such as cotton, linen, paper, rayon, and proteinaceous materials, such as wool and silk, cellulosic materials being preferred. The process of the present invention is particularly effective for the modification of cellulosic materials to increase the resistance of such materials to shrinkage, burning and wrinkling. The textile materials may be in any convenient form such as fiber, thread, yarn, woven fabric, non-woven fabric or knitted fabric. At the time of treatment, the fabric may be in the unfinished state or it may have been previously bleached, dyed and/or printed or otherwise treated.

The modification of textile properties which are achieved in accordance with the present invention apparently result from a crosslinking reaction wherein the vinyl phosphorus compounds of the present invention function as crosslinking agents, reacting with the functional groups of the textile being treated, such as the hydroxyl groups of cellulose. The reactivity of the vinyl groups of the compounds of this invention is increased by their position adjacent to the meta directing P=O group.

Either divinylor trivinylphosphine oxides of the formula may be employed as modifying agents in the present process. Suitable divinyl compounds include those wherein R is hydrogen or a lower alkyl or alkenyl radical of up to four carbon atoms. Trivinylphosphine oxides, since they contain a greater number of reactive sites, are preferred.

The polyvinylphosphine oxides of the present invention may be prepared by the reaction of the corresponding polyvinylphosphine with a suitable oxidizing agent, such as dilute hydrogen peroxide in the manner indicated by the following equation:

The reactivity of the polyvinylphosphine oxide compound is substantially the same when there is present in the compound a substituent such as a lower alkyl radical of about one to four carbon atoms on the ot-vinyl carbon, that is the carbon atom adjacent the phosphorus. However, reactivity is lowered by the presence of substituents other than hydrogen on the fl-vinyl carbon. The lower reactivity of such compounds may be due, at least in part, to steric hinderance. The lower order of reactivity of the fi-substituted vinyl phosphine oxides may also be due to the greater acidity of such compounds, relative to the asubstituted vinyl phosphine oxides, resulting from a greater degree of resonant stabilization of the conjugate base. This greater acidity may result in partial or complete neutralization of the required basic catalyst as well as the conversion of the phosphine oxide to a less reactive form, that is the conjugate base, thereby interfering with the desired alkylation reaction. Because of their lower reactivity, polyvinylphosphine oxides having substituents other than hydrogen on the B-vinyl carbon are considered unsuitable for the process of the present invention.

Typical, nonlimiting examples of polyvinylphosphine oxides which may be employed as modifying agents for textile materials in accordance with the present invention include: trivinylphosphine oxide; divinylphosphine oxide; methyl divinylphosphine oxide; tri-l-methylvinylphosphine oxide (triisopropenylphosphine oxide); di-l-methylvinylphosphine oxide; methyl di-l-methylvinylphosphine oxide; tri-l-ethylvinylphosphine oxide; butyl di-l-ethylvinylphosphine oxide; tri-l-butylvinylphosphine oxide; propyl di-lbutylvinylphosphine oxide; l-methylvinyl di1-prOpylph0S- phine oxide; l-methylvinyl divinylphosphine oxide. The preferred compound for purposes of the present invention is trivinylphosphine oxide.

Textiles modified in accordance with the present inven* tion exhibit a marked increase in wrinkle resistance which is retained even after repeated laundering. No appreciable change is effected in the hand or feel of the materials. Further, the novel modifying agents described herein do not cause retention of chlorine in the treated fabric. Thus, loss of tensile strength, due to chlorine damage, a problem encountered with many known modifying agents, is avoided. In addition, the present process imparts the property of flame resistance to the treated material.

The polyvinylphosphine oxide may be applied to the material in any suitable formulation, for example, as an emulsion or, preferably, as a solution and may be conveniently applied by dipping, spraying, rolling or with the use of a textile pad or other suitable means. After application the excess may be removed by squeezing, centrifuging, pressing, or other operation, and, if desired, the material may be dried by any convenient method, such as in a forced air oven, under infrared lamps, or by evaporation in air at room temperature. The treated cloth is then cured, that is, reacted with the modifying agent, by holding it for a period of time which may vary from less than a minute at elevated temperatures, to several hours at room temperature. As is the case with most textile modifying agents, the addition of excessive amounts may result in a decrease in tensile strength of the treated material, the tensile strength being an inverse function of the amount of modifying agent employed. For low percentages of the present modifying agents the loss in tensile strength is negligible. For practical purposes, the concentration is such as to result in a low loss of tensile strength and high wrinkle resistance, shrink resistance and flame resistance.

Based on the foregoing considerations, an add-on of between about 1 percent and 20 percent by weight of the modifying agent is satisfactory for most purposes. The term add-n as employed herein, refers to the modifying agent which has reacted with the textile material, that is, the modifying agent which remains as an integral chemical part of the textile material, after curing and washing to remove unreacted excess. The amount of addon is given in percent by weight based on the original dry weight of the textile material. For example, where the treatment after curing and washing results in a 10 gram increase in weight for textile sample having an original dry weight of 100 grams, a 10 percent add-on is indicated.

Good stabilization against shrinkage may be obtained with an add-on of between about 1 percent and percent of the modifying agent. An add-on of between about 3 percent and percent imparts excellent wrinkle resistance and at add-ons of between about 5 percent and percent good flame resistance is provided. For best modification of properties an add-on of between about 5 percent and 10 percent is preferred. The add-on percentages mentioned are intended to be instructional and not limitative since higher or lower percentages may be employed, under appropriate circumstances, if desired.

The proportion of modifying agent in the treating formulation may vary considerably. Generally, the proportion will be such as to provide, after application and before curing, a textile material having applied thereto between about 1 percent and 40 percent and preferably between about 10 percent and 20 percent by Weight of the modifying agent, based on the original, dry weight of textile material.

The amount of modifying agent applied to the material may be conveniently controlled by controlling the concentration of modifying agent in the formulation and the degree of wet pick-up. The term wet pick-up indicates the percent of formulation remaining on the material, before curing, after applying and removing excess, based on the original dry weight of the material. Thus, a 100 percent wet pick-up represents an amount of formulation equal to the original dry weight of the textile material. The removal of excess formulation, as by squeezing, may be controlled to provide the desired wet pick-up. Based on a 100 percent wet pick-up, suitable formulations may contain between about 1 percent and 40 percent and preferably 'between about 10 percent and 20 percent by weight of modifying agent.

It is preferred to formulate and apply the modifying agent in aqueous solution. However, if desired, an emulsion or a solution in a suitable nonaqueous solvent, such as alcohol, acetone dioxane, dimethylformamide and the like, or a mixture of such non-aqueous solvent and water, may be employed.

A basic catalyst is employed to assist the reaction between the polyvinylphosphine oxide and the textile material. The basic catalyst may be incorporated as a component of the treating formulation to provide a formulation having a pH greater than 7.0. Preferably, the pH of the treating formulation is between about 8.0 and 11.0. Alternatively, the catalyst may be applied in a separate step either before or after the application of the polyvinylphosphine oxide.

Basic catalysts which may be employed include, for example, alkali metal and other suitable hydroxides, salts of a weak acid and strong base, and quaternary ammonium hydroxides. More specifically, suitable catalysts ininclude the alkali metal carbonates and bicarbonates, such as sodium or potassium carbonate and sodium or potassium bicarbonate, alkali metal hydroxide, alkali metal acetates, phosphates, and metasilicates, tetraalkylammonium hydroxides, and other compounds which, when added to water, increase the pH to greater than 7.0. The amount of catalyst may vary cansiderably. The catalyst is preferably employed in an amount of between about 0.5 percent and 20 percent by weight of the formulation when the application is controlled to provide approximately percent wet pick-up on the fabric. Adjustment of the upper or lower limts of this preferred range of catalyst concentration may be made when different wet pick-up ratios are employed.

After application and removal of excess formulation, the treated material is cured by holding at a temperature between about room temperature (20 degrees centigrade) and about 250 degrees centigrade for a period of time sufiicient to permit the reaction between the phosphorus compound and the textile material to take place. The period of time may range from several hours at room temperature to less than one minute at elevated temperatures. The effectiveness of a cold cure, that is, at about room temperature, may depend to some extent on the nature and concentration of the catalyst employed. If the material is to be cold cured, a strong; ly basic solution, e.g., 10 percent sodium hydroxide is recommended. For elevated temperatures from about degrees centigrade to 250 degrees centigrade, a dilute solution, e.g., 1 percent of an alkali metal hydroxide or weaker base, is satisfactory. It is desirable that the curing temperature is not so high nor the curing time so long as to cause significant damage to the textile material. It has been found that most satisfactory results are achieved at a curing temperature of between about degrees centigrade and degrees centigrade for a period of between about 3 minutes and 10 minutes.

If desired, the treatment with the polyvinylphosphorus compounds of this invention may be supplemented by a treatment with a hand modifier or builder, softener, water-repellent agent, dyestuif, or other material which may further enhance wrinkle resistance or impart or improve other desirable properties. Such additional modifying agents may be applied simultaneously, in the same formulation as the polyvinylphosphorus compound, or they may be applied to the fabric before or after the application of the polyvinylphosphorus compound in a separate operation.

The following specific examples will serve to further illustrate the present invention and the manner in which it may be practiced. All parts are by weight and all temperatures are in degrees centigrade, unless otherwise indicated.

PREPARATION OF MODIFYING AGENTS Example 1 To a solution of 2.2 parts of trivinylphosphine in 20 parts of acetone were gradually added, with stirring, and under a nitrogen atmosphere, 10.3 parts of a solution of 6.8 percent by weight aqueous hydrogen peroxide. The rate of addition was controlled so as to maintain the reaction temperature in the range of 45-55 degrees centigrade. The reaction solution was heated for an additional 45 minutes at about 60 degrees centigrade, after which aliquots were taken which gave a positive test for hydrogen peroxide (titanium sulfate test) and a negative test for trialkylphosphine (methyl iodide test). The reaction solution was then concentrated to dryness, yielding 2.2 parts of a white solid which melted at about 100 degrees centigrade. Sublimation of a 0.5000 gram portion of this material at about 75 degrees centigrade and 0.25 millimeter of mercury, absolute pressure, yielded 0.3936 gram of pure trivinylphosphine oxide, having a melting point of 98 degrees centigrade to 100 degrees centigrade. Thus, the yield of pure trivinyl phosphine oxide equaled 67 percent.

AnaIysis.Calcd for C H PO (percent): C, 56.25; H, 708; P, 24.18. Found (percent): C, 56.13; H, 6.87; P, 24.28.

Following the general procedure of the above example, tri-l-methylvinylphosphine oxide is prepared by the addition of 50.5 parts of a 6.8 percent by weight hydrogen peroxide solution to a solution of 15.4 parts of tri-lmethylvinylphosphine in 300 parts of acetone.

Example 2 A solution of 22 parts of trivinylphosphine in 160 parts of acetone was reacted with a solution of 22.6 parts of 30 percent by weight hydrogen peroxide and 80 parts of water, as in Example 1. Vacuum removal of solvents resulted in recovery of a 75 percent yield of crude trivinylphosphine oxide, as a moist white solid.

Following the general procedure of the above example, l-methylvinyl di-l-propylvinylphosphine oxide is prepared by the reaction of 21.0 parts of l-methylvinyl di-lpropylvinylphosphine in 400 parts of acetone with 50.5 parts of a 6.8 percent by weight aqueous solution of hydrogen peroxide.

TEXTILE TREATMENT Example 3 A switch of bleached, desized, mercerized, 80 x 80 (threads per inch) cotton print cloth, weighing 3.1 ounces per square yard, was soaked in an aqueous solution containing 12.5 percent by weight of trivinylphosphine oxide and 6.25 percent by weight sodium carbonate and then was squeezed through the rolls of a laboratory textile padder to effect about an 80 percent wet pick-up. The swatch was then cured by heating for 10 minutes at 160 degrees centigrade in a forced air textile type of oven. The treated fabric was hand washed in hot, soapy water, rinsed, pressed dry and flat, and equilibrated to laboratory conditions. The add-on was 6.5 percent. The wrinkle recovery angles, a measure of the ability of a material to recover from wrinkles, were determined. The wrinkle recovery angles (fill direction) were found to be 120 degrees, dry, and 116 degrees, wet, compared to 82 degrees, dry, and 84 degrees, wet, for an untreated control. In a test for flame resistance, strips of treated fabric, held in a horizontal position, were ignited. After removal of the flame source, the flame went out and the strips were free from afterglow.

The replacement of the aqueous solution of trivinylphosphine oxide in the above example, with an aqueous solution of tri-l-methylvinylphosphine oxide, results in a cloth having comparable wrinkle resistance and flame resistance.

Example 4 A swatch of cotton print cloth was soaked in a pad bath containing 20 percent by weight trivinylphosphine oxide and 6.25 percent by weight sodium carbonate, squeezed to about 80 percent wet pick-up and cured for 10 minutes at 160 degrees centigrade. The treated swatch was washed in hot, soapy water, rinsed, pressed dry and flat, and equilibrated to ambient conditions.

The wrinkle recovery angles (fill direction) of the swatch were found to be 115 degrees, dry, and 130 degrees, wet. The add-on was 9.65 percent by weight and the phosphorus content was 1.77 percent. The treated swatch was boiledv for about 5 hours in a strong solution of sodium carbonate (0.25 percent), a commercial flaked mixed sodium and potassium solid unbuilt soap of fatty acids essentially of 10 to 18 carbon atoms (0.25 percent), and a commercial heavy duty built synthetic organic detergent (0.025 percent). An analysis of the swatch, after the boiling treatment, showed no loss in phosphorus and wrinkle recovery values were 121 degrees, dry, and 135 degrees, wet.

The replacement of the pad bath containing trivinylphosphine oxide, in the above example, with a pad bath containing methyl divinylphosphine oxide, also results in a cloth showing substantially improved wrinkle resistance.

Example 5 A swatch of cotton print cloth was soaked in a 15 percent by weight aqueous solution of trivinylphosphine oxide, squeezed to about percent wet pick-up, dried for 2 minutes at 93 degrees centigrade and then passed through rollers which were wetted with a 10 percent aqueous solution of sodium hydroxide, so as to obtain an approximately 80 percent wet pick up of the aqueous base. The wet cloth was wrapped in plastic film, stored 18 hours at ambient temperature, then hand washed in hot, soapy water, rinsed, pressed, and equilibrated to laboratory conditions. The add-on of trivinylphosphine oxide was found to be 2.1 percent. The treated cloth displayed a wet wrinkle recovery value of degrees, compared with 84 degrees for the untreated control, the improvement in wet wrinkle recovery, in this example, having been effected by curing without application of heat.

Example 6 The procedure of Example 3 was repeated with the exception that the treating solution consisted of 15 percent by weight of trivinylphosphine and 3.3 percent by weight sodium bicarbonate and the cure was effected over a period of 3 minutes at degrees Centigrade. The washed, equilibrated fabric had a 6.1 percent by weight add-on of trivinylphosphine oxide and displayed a wet wrinkle recovery value (fill direction) of 111 degrees, compared to about 84 degrees for the untreated control.

Example 7 A swatch of white, worsted 100 percent wool fabric was passed through a textile pad containing an aqueous solution containing 2 percent of trivinylphosphine oxide and 1 percent of a commercial nonionic wetting agent (Triton 100), squeezed to about 75 percent wet pick-up, placed on a pin frame and cured for 10 minutes at 182 degrees centigrade. A second swatch of wool, which served as a control, was treated identically except that the treating solution contained none of the trivinylphosphine oxide component. Both swatches were put through various, but identical washing and drying operations, after which it was found that the swatch treated with the solution containing the trivinylphosphine oxide exhibited a noticeably greater resistance to shrinkage than the control swatch.

Example 8 Swatch 8-A Swatch 8-13 Add-on (percent) 8. 5 8. 1 Dry wrinkle recovery fill (degrees) 116 00 Wet wrinkle recovery fill (degrees) 147 141 Example 9 A swatch of cotton print cloth, designated as sample 9-A, was passed through a textile pad containing an aqueous solution of 20 percent by weight of trivinylphosphine oxide and 5.5 percent by weight of sodium carbonate, squeezed to about 80 percent wet pick-up, cured for one minute at 121 degrees centigrade on a pin frame and cured for 3 minutes at 182 degrees Centigrade on a pin frame. The treated fabric was hand washed in warm, soapy water, rinsed, pressed flat and dry, and equilibrated to laboratory conditions. A second swatch of the same material, designated as sample 9-B, was similarly treated except that the treating solution contained 15 percent by weight of trivinylphosphine oxide and 4.15 percent by weight of sodium carbonate. A third swatch of the same material, and designated as sample 9C, was similarly treated except that the treating solution contained 10 percent by weight of trivinylphosphine oxide and 2.74 percent by weight of sodium carbonate. The treated fabrics, plus an untreated swatch of the same material, were subjected to five hand-wash drip-dry treatments, then two machine-wash drip-dry treatments, then two machine-wash tumble-dry treatments and finally two machine-wash line-dry treatments following generally the washing procedure (wash water temperature 42 degrees centigrade) and wash-and-wear evaluation described in the American Association of Textile Chemists and Colorists Tentative Test 88-1958 (using low angle lighting). Testing of the three treated samples and the untreated sample yielded the following data:

Wash-and-wear ratings A portion of swatch 9-B, after havingbeen washed repeatedly as described above, was bleached white with hydrogen peroxide solution and then was subjected to a chlorine bleaching and scorching test (Test 92-1962 of the American Association of Textile Chemists and Colorists) to determine damage by retained chlorine. There was no loss of tensile strength due either to the bleaching or the bleaching and scorching treatments. Other portions of the same multiwashed sample 9-B displayed flame resistance as demonstrated in Example 3. Another portion of the multiwashed sample 9-B, after grind ing through a 20-mesh screen (0.3-inch openings), using a rotary knife cutter, was found to be substantially insoluble in cuprammonium hydroxide solution. This insolubility indicates that the treatment with trivinylphosphine oxide caused cross-linking of the cellulose fibers.

Following the general procedure of 'Examples 3 through 9, divinylphosphine oxide; dimethylvinylphosphine oxide; l-methylvinyl di-l-propylvinylphosphine oxide, and l-methylvinyl divinylphosphine oxide, employed in place of the polyvinylphosphine oxides described, produce textile materials with improved wrinkle resistance.

It will be apparent to those skilled in the art that many variations and modifications of the invention as hereinabove set forth may be made without departing from the spirit and scope of the invention. The invention is not to be construed as being limited only to the examples given.

What is claimed is:

1. A method for imparting a high degree of wrinkleresistance to textile materials having functional groups capable of reaction with activated vinyl groups which comprises reacting said textile material, in the presence of 8 a basic catalyst, with a polyvivnylphosphine oxide having the structural formula:

R1 0 R: Omaha.

it. wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl radicals and R is selected from the group consisting of hydrogen, lower alkyl and vinyl radicals.

2. A method according to claim 1 wherein said polyvinylphosphine oxide and said catalyst are separately applied to the textile material.

3. A method according to claim 1 wherein said polyvinylphosphine oxide is trivinylphosphine oxide.

4. A method according to claim 3 wherein said textile material is a cellulosic material.

5. A method for imparting a high degree of wrinkle resistance to textile materials having functional groups capable of reaction with activated vinyl groups which comprises the steps of:

(A) contacting said textile material with a formulation comprising a basic catalyst and a polyvinyl phosphine oxide having the structural formula:

wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl groups, and R is selected from the group consisting of hydrogen, lower alkyl and vinyl radicals, said polyvinyl phosphine oxide being present in an amount sufficient to provide from about 1 to about 40 percent of the textile material;

(B) removing excess formulation, and

(C) curing the treated material by maintaining said treated material at a temperature between about 20 and about 250 degrees centigrade for a period sufficient to eifect reaction between said textile material and said polyvinyl phosphine oxide.

6. A method according to claim 5 wherein said material is a cellulosic material.

7. A method according to claim 6 wherein the amount of polyvinylphosphine oxide remaining on said material after removal of excess formulation is between about 10 percent and 20 percent by weight, based on the original dry weight of said material and said material is subsequently cured for a period of from about 3 minutes to 10 minutes at a temperature of between about degrees centigrade and degrees centigrade.

8. A method according to claim 7 wherein said formulation comprises an aqueous solution of trivinylphosphine oxide having a pH between about 8.0 and 11.0.

9. An improved textile material having a high degree of wn'nkle resistance comprising a textile material ha ing functional groups capable of reaction with activated vinyl groups reacted with between about 1 and about 20 percent by weight of a polyvinyl phosphine oxide having the formula:

R1 0 R2 (raped-5:011, 1'1.

wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl radicals, and R is selected from the group consisting of hydrogen, lower alkyl and vinyl radicals.

10. An improved textile material according to claim 9 wherein said material is cellulosic and said polyvinylphosphine oxide trivinylphosphine oxide.

11. An improved textile material according to claim 10 wherein said material is reacted with between about 5 percent and 10 percent by weight of trivinylphosphine oxide.

12. An alkaline formulation for imparting a high degree of wrinkle resistance to textile materials having functional groups capable of reaction with activated vinyl groups comprising a basic catalyst and 140% by weight of a polyvinyl phosphine oxide of the formula:

wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl radicals, and R is selected from the group consisting of hydrogen, lower alkyl and vinyl radicals.

13. A formulation according to claim 12 which comprises an alkaline, aqueous solution and said polyvinylphosphine oxide is present in an amount between about 1 percent and 40 percent by weight.

1 4. A formulation according to claim 13 which comprises between about 10 percent and 20 percent by weight of trivinylphosphine oxide.

References Cited February 1956, Textile Research Journal, pp. 156-166.

Fireproofing of Polymers with Derivatives of Phosphines and With Halogen-Phosphorus Compounds, Boyer and Vajda, SPE Transactions, January 1964, vol. 4, No. 1, pp. 45-55.

Preparation of Triallylphosphine Oxide, Chance & Guthrie, J. Appl. Chem, 10, October 1960.

GEORGE F. LESMES, Primary Examiner M. B. WITTENBERG, Assistant Examiner US. Cl. X.R. 

